Effect of metallic cations on the sorption of pesticides on soil

We studied the adsorption and desorption of two pesticides, namely isoproturon and dimetomorph, onto a model soil sample. We first show that the adsorption of isoproturon depends on pH, from 1 mg g⁻¹ at pH 4 to 2 mg g⁻¹ at pH 10, contrary to the adsorption of dimetomorph (5.8 mg g⁻¹). We also studied the influence of metallic cations, copper(II), iron(III), manganese(II), and chromium(III), on the sorption of isoproturon and dimetomorph. We found that in the case of isoproturon, the presence of metallic cations does influence the retention capacity of the soil sample. The sorption becomes very weak in the presence of copper and chromium, whereas in the case of iron and manganese the sorption properties are slightly modified.     

Adsorption of cationic and anionic surfactants onto organic polymer resin Lewatit VPOC 1064 MD PH

The adsorption of a cationic (CTAB, cetyl trimethylammonium bromide) and an anionic surfactant (SLES, sodium dodecylethersulfate) from aqueous solution onto organic polymer resin (Lewatit VPOC 1064 MD PH) was studied. A series of batch experiments were performed to determine the sorption isotherms of surfactants to organic polymer resin. The experimental studies were analyzed by Langmuir and Freundlich isotherms. Furthermore, the isotherm parameters, average percentage errors (ε) of model data, and separation factor (R _L) were calculated. Other factors influencing the adsorption capacity (contact time, adsorbent amount, and initial surfactant concentration) were also discussed. The experimental data fitted very well to the Langmuir equilibrium model in the studied concentration range. The calculated R _L values showed that the adsorption of both surfactants were favorable. Among the surfactants, CTAB showed higher adsorption capacity onto organic polymer resin compared to SLES (Q ⁰ = 250 and 34.36 mg g⁻¹, respectively).     

Capacity of simultaneous removal of zinc and cadmium from contaminated media, by two microalgae isolated from a polluted site

Several aquatic environments have been contaminated with heavy metals dumped via industrial effluents. Numerous studies have been published regarding the removal of single metals from aqueous solutions by microalgal biomass. However, such studies do not reflect the actual problem associated with industrial effluents because usually more than one metal species is present. Here we studied the biosorption capacity of Zn²⁺ and Cd²⁺ as single- and binary-metal systems by two microalgae, Scenedesmus obliquus and Desmodesmus pleiomorphus, isolated from a polluted site in Northern Portugal. For each metal independently, D. pleiomorphus showed a higher metal sorption capacity than S. obliquus, at concentrations ranging from 60 to 300 mg/l (except 150 mg_Cd/l). Maximum amounts of Zn²⁺ and Cd²⁺ removed were 22.3 and 60.8 mg/g by S. obliquus, and 83.1 and 58.6 mg/g by D. pleiomorphus. In binary-metal solutions, S. obliquus was in general able to remove Zn²⁺ to higher extents than Cd²⁺, whereas the opposite was observed with D. pleiomorphus. The simultaneous uptake of Zn²⁺ and Cd²⁺ by both microalgae was considerably lower than that of their single-metal counterparts, at equivalent concentrations. Although microalgal uptake from binary-metal solutions was lower than from single-metal ones, the wild microalgae selected were able to efficiently take up mixtures of Zn²⁺ and Cd²⁺ up to 300 mg/l of both metals—thus materializing a promising bioremediation vector for polluted waters.     

Experimental determination of Cd2+ adsorption mechanism on low-cost biological waste

Carbonate shells have an astonishing ability in the removal of Cd²⁺ in a short time period with emphasis on being a low cost adsorbent. In the present study, the sorption capacity of carbonate shells was studied for Cd²⁺ in batch experiments. The influence of different carbonate shell sizes and physico-chemical factors were evaluated and the results were analyzed for its correlation matrices by using Predictive Analytics Software (PASW). The mineralogy state of aqueous solution regarding the saturation index was simulated using PHREEQC to identify the Cd²⁺ uptake mechanism. The Cd uptake rates were calculated as well as Ca²⁺, HCO ₃ ^? concentration, pH, ambient humidity and temperature were measured. Cd²⁺ removal of 91.52% was achieved after 5 h adsorption. The adsorption efficiencies were significantly influenced by pH as they increased with the increase of pH from acidic solution (5.50±0.02) to slightly alkaline (7.60±0.05). In addition, the mineralogy state of aqueous solution calculated from PHREEQC confirmed that the increment of Ca²⁺ and HCO ₃ ^? concentrations in solution was attributed to the dissolution of carbonate shells. Moreover, the ion exchange adsorption mechanism of Cd²⁺ toward Ca²⁺ was identified as the process involved in Cd²⁺ uptake.     

High removal of phosphate from wastewater using silica sulfate

This report shows that silica sulfate is removing phosphate from wastewater very efficiently. Phosphorus removal and recovery from wastewater is a worldwide issue due to pollution of natural waters by phosphate and depletion of phosphate ores. Adsorption is a process that can remove phosphate at low concentrations. Adsorption also allows the recovery of phosphate for possible re-use. Here, we studied the adsorption of phosphate from wastewater using commercial Zr ferrite, Zr-MCM 41 and silica sulfate. We calculated equilibrium isotherms, kinetic models and thermodynamic effects under conditions similar to real wastewaters. We found that the equilibrium data for the adsorption of phosphate were best fitted to the Freundlich model. The results show that the maximum uptake of phosphate was 3.36 mg g⁻¹ for Zr-MCM, 27.73 mg g⁻¹ for Zr ferrite and 46.32 mg g⁻¹ for silica sulfate. The kinetic results of the three adsorbents were satisfactorily predicted using a pseudo-second-order model. We found that silica sulfate provided excellent characteristics in terms of the maximum adsorption and rate constant for the adsorption of phosphate. The thermodynamic data showed that increasing the temperature enhanced the adsorption of phosphate onto silica sulfate. Our findings will help to define efficient methods to remove phosphate from wastewater.     

Inhibition of Na+/K+-ATPase and of active ion-transport functions in the gills of the shore crab Carcinus maenas induced by cadmium

Inhibition of Na⁺/K⁺-ATPase from gill plasma membranes of the shore crab Carcinus maenas by cadmium was investigated and compared with inhibitory effects by known antagonists (ouabain and Ca²⁺). For comparative considerations the Cd²⁺-inhibition of the enzyme from dog kidney was also tested. Na⁺/K⁺-ATPase from dog kidney and from crab gill differed greatly in sensitivity against ouabain. The inhibition constant K _i of the dog enzyme amounted to 9.1 × 10⁻⁷ mol l⁻¹, i.e. more than 300-fold smaller than the K _i of 2.9 × 10⁻⁴ mol l⁻¹ determined for the crab enzyme. Ca²⁺ inhibited the activity of Na⁺/K⁺-ATPase from crab gill plasma membranes with a K _i of 4.3 × 10⁻⁴ mol l⁻¹. The Na⁺/K⁺-ATPase from crab gill was inhibited by Cd²⁺ with a K _i of 9.1 × 10⁻⁵ mol l⁻¹. Cd²⁺ inhibited the Na⁺/K⁺-ATPase from dog kidney with a K _i (6.4 × 10⁻⁵ mol l⁻¹) comparable to that observed in the crab gill enzyme. Under experimental conditions Cd²⁺-inhibition of Na⁺/K⁺-ATPase was irreversible. Repeated washing, centrifugation and homogenization of the plasma membranes (four times) with Cd²⁺-free buffer did not restore any activity lost in the presence of 1 × 10⁻³ mol l⁻¹ Cd²⁺. Since ouabain-insensitive (nonspecific) ATPases in the plasma membrane fraction of crab gills were inhibited by Cd²⁺ in the same way as Na⁺/K⁺-ATPase, the heavy metal is considered as an unspecific ATPase inhibitor. Comparing these results with literature data on Cd²⁺-binding to electrophoretically separated proteins suggests that Na⁺/K⁺-ATPase is a Cd²⁺-binding enzyme. The results obtained on Na⁺/K⁺-ATPase were reflected by Cd²⁺-inhibition of the branchial ion-transport functions depending on this enzyme. The transepithelial short-circuit current of isolated gill half lamellae, a direct measure of area-specific active ion uptake, and the transepithelial potential difference of isolated, perfused whole gills, also indicative of active ion uptake, were inhibited by the heavy metal in a time- and dose-dependent mode. Remarkably these inhibitions were also irreversible. These findings are ecologically and biomedically significant: even when the actual environmental or tissue concentrations measured are low, biological microstructures such as Na⁺/K⁺-ATPase may accumulate the heavy metal by tight binding over prolonged periods until the first inhibitory effects occur. Received: 25 June 1997 / Accepted: 25 August 1997     

Removal of heavy metals from aqueous solutions using activated carbon prepared from Cicer arietinum

Removal of Cu²⁺, Cd²⁺, Pb²⁺, and Zn²⁺ from aqueous solutions by activated carbon prepared from stems and seed hulls of Cicer arietinum, an agricultural solid waste, has been studied. The influence of various parameters, such as pH, contact time, adsorbent dose, and initial concentration of metal ions on removal was evaluated. The activated carbon was characterized by FT-IR spectroscopy, X-ray diffraction, and elemental analysis. Sorption isotherms were studied using Langmuir and Freundlich isotherm models. All experimental sorption data were fitted to the sorption models using nonlinear least-squares regression. The maximum adsorption capacity values for activated carbon prepared from Cicer arietinum waste for metal ions were 18 mg g^?1 (Cu²⁺), 18 mg g^?1 (Cd²⁺), 20 mg g^?1 (Pb²⁺), and 20 mg g^?1 (Zn²⁺), respectively. The Freundlich isotherm model fit was best, followed by the pseudo-second-order kinetic model. Desorption studies were carried out with dilute hydrochloric acid for quantitative recovery of the metal ions and for regeneration of the adsorbent.     

Adsorption of vanadate(V) on Fe(III)/Cr(III) hydroxide waste

Adsorption of vanadate(V) from aqueous solution onto industrial solid ‘waste’ Fe(III)/Cr(III) hydroxide was investigated. HCl treated Fe(III)/Cr(III) hydroxide was found to be more efficient for the removal of vanadate(V) compared to untreated adsorbent. The adsorption follows second-order kinetics. Langmuir and Freundlich isotherms have been studied. The Langmuir adsorption capacity (Q ₀) of the treated and untreated adsorbents was found to be 11.43 and 4.67 mg g⁻¹, respectively. Thermodynamic parameters showed that the adsorption process was spontaneous and endothermic in the temperature range 32–60°C. Maximum adsorption was found at system pH 4.0. The adsorption mechanism was predominantly ion exchange. Effect of other anions such as phosphate, selenite, molybdate, nitrate, chloride, and sulfate on adsorption of vanadium has been examined.     

Effect of low molecular weight organic acids on adsorption and desorption of fluoride on variable charge soils

The effect of four low molecular weight organic acids on F⁻ adsorption by two variable charge soils was investigated using a batch method. The organic acids reduced F⁻ adsorption through competition by the acids with F⁻ for sorption sites. Oxalic and malonic acids, both of which have simpler chemical structures, were more effective than citric or malic acid. The effect of organic acids on F⁻ adsorption was more prominent at higher pH values and with larger amounts of the organic acids. The desorption study showed that the organic acids enhanced the desorption of F⁻ adsorbed by the soils. In the control and malic acid systems, desorption increased sharply with decreasing pH, while in the oxalic acid system, desorption rose slightly with decreasing pH. Desorption also increased with increasing amount of organic acid added. There are two possible mechanisms for the effect of the organic acids on F⁻ adsorption and desorption: (1)␣competition of the organic acids with F⁻ for adsorption sites and (2) dissolution of the adsorbents, especially dissolution of soil Al.     

Inorganic mercury and methylmercury in surface sediments and mussel tissues from a microtidal lagoon (Bizerte, Tunisia)

The aim of this study was to investigate the distribution of mercury compounds in marine sediments and mussel tissues collected in the lagoon of Bizerte, Tunisia, during two seasons (summer and winter). Inorganic mercury (Hg²⁺) concentrations in sediments were found to be highly variable, ranging from 0.04 nmol.g¹ to 3.22 nmol.g⁻¹ (dry weight) with a mean value of 0.52 nmol.g⁻¹. Anthropogenic sources of Hg²⁺, most probably metallurgy or tire production industries, have been evidenced. The mean concentration of monomethylmercury (MeHg⁺) in the surface sediments is 2.32 pmol g⁻¹ ranging from below the detection limit (0.45 pmol.g⁻¹) to 14.6 pmol.g⁻¹. No significant variation was observed between winter and summer seasons for both mercury species concentration in the sediments. The Hg²⁺ concentrations in mussel tissues are also variable, ranging from 0.007 to 1.347 nmol.g⁻¹ (dry weight). The mean concentration is 0.70 nmol.g⁻¹. In these tisssues, Hg²⁺ is generally the major compound, making up ca. 88% of total mercury concentrations. However, methylmercury concentrations are significant and homogeneous, ranging from 62 to 121 pmol.g⁻¹ (mean 96 pmol.g⁻¹). The results suggest that a fraction of the inorganic mercury load in the sediments of the lagoon undergoes methylation pathways. MeHg⁺ produced is assimilated in the mussels more readily than Hg²⁺.     

Feeding on intertidal microbial mats by postlarval tiger shrimp, <Emphasis Type="Italic">Penaeus semisulcatus</Emphasis> De Haan

A series of experiments investigated the potential role of microbial mats in nutrition of the early settlement stages of Penaeus semisulcatus. From 3 days post-metamorphosis, the microbial mat supported high growth and survival rates in postlarvae, equivalent to that supported by a control diet of Artemia nauplii and mussel. Examination of gut contents indicated that benthic postlarvae feed indiscriminately on the microbial mat. However, when postlarvae were fed separated size-fractions of the microbial mat, only the fraction containing a high concentration of infauna (mainly nematodes) was able to support the same growth as intact microbial mat. This appears to be due to the low nitrogen content (0.4–0.9 mmol g⁻¹) of the various size-fractions, compared to that of infauna (4.0 mmol g⁻¹). The stable isotope composition of the dietary size-fractions and postlarval shrimp tissue supports the hypothesis that the shrimp assimilated C and N primarily from the associated infauna. This may be due to selective feeding that is not apparent from stomach contents, due to rapid digestion of fauna soft tissues, or to differential assimilation of infaunal prey relative to other microbial mat components. The results demonstrate that microbial mats may support survival and growth in early-stage penaeid shrimp postlarvae on intertidal mud flats.     

Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.     

Synthesis and characterization of Fe-MCM-41 from rice husk silica by hydrothermal technique for arsenate adsorption

Rice husk (RH) agro-waste was used as a raw material for synthesizing mesoporous molecular sieves, MCM-41. The Fe-MCM-41 was prepared by the hydrothermal technique (HT), resulting in a higher surface area and crystallinity than when prepared under ambient conditions. In addition, a hexagonal structure was clearly seen with hydrothermal technique (HT) preparation. The adsorption of arsenate by HT-Fe-MCM-41 was investigated. The factors studied affecting arsenate adsorption capacity were ferric content in MCM-41, contact time, pH of solution, and initial arsenate concentration. It was found that HT-Fe-MCM-41 at the Si/Fe mole ratio of 10 gave the highest adsorption capacity. Arsenate adsorption reached equilibrium within 4 h. The adsorption capacity of HT-Fe-MCM-41 (Si/Fe = 10) was affected by the initial pH value and the initial arsenate concentration. The adsorption capacity was highest at pH 3 and decreased thereafter with increases in the pH of solution value. The Langmuir model fit the arsenate adsorption isotherm well. The maximum adsorption capacity for arsenate was 1,111 μg g⁻¹.     

Uptake of Ni2+ and rhodamine B by nano-hydroxyapatite/alginate composite beads: batch and continuous-flow systems

Alginate encapsulated nano-hydroxyapatite beads were synthesized and characterized by Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller surface analysis, and X-ray diffraction. Their adsorptive potential for Ni²⁺ and rhodamine B was explored in batch mode and by fixed-bed column passage. In the batch system, maximum uptake capacity for Ni²⁺ was 360 mg g^?1 and 480 mg g^?1 for rhodamine B. In the presence of humic acid, sorption was enhanced. For the continuous-flow system, adsorption was effective at low flow rate. For both pollutants, mass transport resistance increased during adsorption. The overall rates of rhodamine B and Ni²⁺ uptake were found to be controlled by external mass transfer.     

Dimethylsulfoniopropionate and dimethylsulfide in the marine flatworm Convoluta roscoffensis and its algal symbiont

 A distinct smell of dimethylsulfide (DMS) was noted at the edge of the intertidal mudflat of Marennes-Oléron Bay, at the French Atlantic coast, where dense populations of the marine flatworm Convoluta roscoffensis Graff (Platyhelminthes: Turbellaria) were present. DMS is the cleavage product of dimethylsulfoniopropionate (DMSP). DMSP was shown to be present in high amounts in sediment containing the flatworm as well as in axenic cultures of the symbiotic alga Tetraselmis sp. that was isolated from the flatworm. In untreated sediment samples containing C. roscoffensis the concentration of DMS was as high as ∼55 μmol l⁻¹ sediment, and in samples that were fixed with glutaraldehyde the concentration of DMS was even three orders of magnitude higher (∼66 mmol l⁻¹ sediment). This rapid cleavage of DMSP to DMS in fixed samples was unexpected. Pure DMSP was stable in glutaraldehyde, and it was therefore concluded that a DMSP-lyase was responsible for cleavage in the field samples. The isolated symbiotic alga, Tetraselmis sp., did not show DMSP-lyase activity, indicating that DMSP-lyase may have been present in the flatworm, although the role of bacteria could not be excluded. The Chl a-specific DMSP content of C. roscoffensis (∼200 mmol g⁻¹) was much higher than that of Tetraselmis sp. (∼30 mmol g⁻¹). Possibly, DMSP was not only present in the symbiotic alga, but was also incorporated in the body tissue of the flatworm. It remains unclear what the function of DMSP is in C. roscoffensis. In Tetraselmis sp., but not in C. roscoffensis, DMSP increased with increasing salinity. It was concluded that salinity probably does not play an important role in the dynamics of DMSP and DMS in sediment containing C. roscoffensis. Received: 21 January 2000 / Accepted: 29 August 2000     

Immobilized Lentinus edodes residue as absorbent for the enhancement of cadmium adsorption performance

To investigate the potential use of Lentinus edodes (L. edodes) residue for Cd²⁺ adsorption, poly alcohol Na alginate (PVA) was applied to immobilize it. The parameters including contact time, pH, adsorbent dosages, and coexisting metal ions were studied. The suitable pH for immobilized L. edodes was 4?C7 wider than that for raw L. edodes (pH 6?C7). In the presence of Pb²⁺ concentration varying from 0 to 30 mg·L^?1, the Cd²⁺ adsorption ratios declined by 6.71% and 47.45% for immobilized and raw L. edodes, respectively. While, with the coexisting ion Cu²⁺ concentration varied from 0 to 30 mg·L^?1, the Cd²⁺ adsorption ratios declined by 12.97% and 50.56% for immobilized and raw L. edodes, respectively. The Cd²⁺ adsorption isotherms in single-metal and dual-metal solutions were analyzed by using Langmuir, Freundlich, and Dubinin-Radushkevich models. The Cd²⁺ adsorption capacities (q _m) in single-metal solution were 6.448 mg·L^?1 and 2.832 mg·L^?1 for immobilized and raw L. edodes, respectively. The q _m of immobilized L. edodes were 1.850 mg Cd·g^?1 in Cd²⁺ + Pb²⁺ solution and 3.961 mg Cd·g^?1 in Cd²⁺ + Cu²⁺ solution, respectively. The Cd²⁺ adsorption processes subjected to both adsorbents follow pseudo-second-order model. Mechanism study showed the functional group of L. edodes was -OH, -NH, -CO, and PVA played an important role in metal adsorbing. Mining wastewater treatment test showed that PVA-SA-immobilized L. edodes was effective in mixed pollutant treatment even for wastewater containing metal ions in very low concentration.     

Residues of fluoroquinolones in marine aquaculture environment of the Pearl River Delta, South China

Concentrations and distributions of selected fluoroquinolones (norfloxacin, ciprofloxacin and enrofloxacin) in water, sediments and nine kinds of fish species collected from 6 sites in two marine aquaculture regions of the Pearl River Delta, China, were analyzed by using high-performance liquid chromatography with fluorescence detector (HPLC). The results showed that the concentrations of ciprofloxacin and enrofloxacin were below the limits of quantification (LOQ) in all water samples except for norfloxacin. Norfloxacin and ciprofloxacin concentrations ranged from 1.88 to 11.20 ng g⁻¹ dry wt, 0.76–2.42 ng g⁻¹ dry wt in sediments collected from the Dapeng’ao region (sites 1–3) and ranged from 2.31 to 4.75 ng g⁻¹ dry wt, 1.26–1.76 ng g⁻¹ dry wt in sediments collected from the Hailing Island region (sites 4–6), respectively. However, no enrofloxacin was found in all sediment samples. The three fluoroquinolones (FQs) were detected in all fish samples, and the concentrations were higher in liver tissues than those in muscle tissues. The levels of norfloxacin were higher than ciprofloxacin and enrofloxacin in both liver and muscle tissues. Among the nine marine fish species, Siganus fuscescens from Hailing Island had a significantly high level of norfloxacin in liver tissue (254.58 ng g⁻¹ wet wt), followed by Sparus macrocephalus (133.15 ng g⁻¹ wet wt) from Dapeng’ao, and the lowest value was Lutianus argentimaculatus (5.18 ng g⁻¹ wet wt) from Hailing Island. The obtained results of FQs in present study do not represent a risk to the human health in Guangdong coastal area, based on the maximum residue limits (MRLs) established by Chinese Government and the acceptable daily intake (ADI) recommended by the Food and Agriculture Organization and World Health Organization (FAO/WHO).     

Presence of Alexandrium catenella and paralytic shellfish toxins in finfish, shellfish and rock crabs in Monterey Bay, California, USA

The central California coast is a highly productive, biodiverse region that is frequently affected by the toxin-producing dinoflagellate Alexandrium catenella. Despite the consistent presence of A. catenella along our coast, very little is known about the movement of its toxins through local marine food webs. In the present study, we investigated 13 species of commercial finfish and rock crabs harvested in Monterey Bay, California for the presence of paralytic shellfish toxins (PSTs) and compared them to the presence of A. catenella and PSTs in sentinel shellfish over a 3-year period. Between 2003 and 2005, A. catenella was noted in 55% of surface water samples (n = 307) and reached a maximum concentration of 17,387 cells L⁻¹ at our nearshore site in Monterey Bay. Peak cell densities occurred in the month of July and were associated with elevated shellfish toxicity in the summers of 2004 and 2005. When A. catenella was present, particulate PSTs were detected 71% of the time and reached a maximum concentration of 962 ng STXeq L⁻¹. Of the 13 species tested, we frequently detected PSTs in Pacific sardines (Sardinops sagax; maximum 250 μg STXeq 100 g⁻¹), northern anchovies (Engraulis mordax; maximum 23.2 μg STXeq 100 g⁻¹), brown rock crabs (Cancer antennarius; maximum 49.3 μg STXeq 100 g⁻¹) and red rock crabs (C. productus; 23.8 μg STXeq 100 g⁻¹). PSTs were also present in one sample of Pacific herring (Clupea pallas; 13.3 μg STXeq 100 g⁻¹) and one sample of English sole (Pleuronectes vetulus; 4.5 μg STXeq 100 g⁻¹), and not detected in seven other species of flatfish tested. The presence of PSTs in several of these organisms reveals that toxins produced by A. catenella are more prevalent in California food webs than previously thought and also indicates potential routes of toxin transfer to higher trophic levels. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Phenanthrene adsorption by soils treated with humic substances under different pH and temperature conditions

The mobility of phenanthrene (PHE) in soils depends on its sorption and is influenced by either the existing soil humus or exogenous humic substances. Exogenous humic acids (HAs) were added to soil to enhance the amount of soil organic carbon (SOC) by 2.5, 5.0, and 10.0 g kg⁻¹. PHE desorption of the treated soils was determined at two pH levels (3.0 and 6.0) and temperatures (15 and 25 °C). Soil PHE adsorption was related to pH and the type and quantity of added HAs. Humic acid (HA) and fulvic acid (FA) derived from peat had different effects on adsorption of PHE. Adsorption increased at first and then decreased with increasing quantity of exogenous FA. When the soil solution pH (in 0.005 M CaCl₂) was 4.5 or 3.0, the turning points were 2.5 g FA kg⁻¹ at pH 3.0 and 5 g FA kg⁻¹ at pH 4.5. When soil solution pH was 6, the amount of adsorbed PHE was enhanced with increasing exogenous HAs (HA or FA) and amount of adsorption by soil treated with FA was higher than with HA. Adsorption of PHE in the FA treatment at 10.0 g kg⁻¹ was lower than the controls (untreated soil or treatment with HAs at 0 g kg⁻¹) when the soil solution pH was 3.0. This suggests that FA adsorbed by soil was desorbed at low pH and would then increase PHE solubility, and PHE then combined with FA. PHE adsorption was usually higher under lower pH and/or lower temperature conditions. PHE sorption fitted the Freundlich isotherm, indicating that exogenous humic substances influenced adsorption of phenanthrene, which in turn was affected by environmental conditions such as pH and temperature. Thus, exogenous humic substances can be used to control the mobility of soil PAHs under appropriate conditions to decrease PAH contamination.     

Sorption and bioavailability of arsenic in selected Bangladesh soils

The bioavailability of arsenic (As) in the soil environment is largely governed by its adsorption–desorption reactions with soil constituents. We have investigated the sorption–desorption behaviour of As in four typical Bangladeshi soils subjected to irrigation with As-contaminated groundwater. The total As content of soils (160 samples) from the Laksham district ranged from <0.03 to approximately 43 mg kg⁻¹. Despite the low total soil As content, the concentration of As in the pore water of soils freshly irrigated with As-contaminated groundwater ranged from 0.01 to 0.1 mg l⁻¹. However, when these soils were allowed to dry, the concentration of As released in the pore water decreased to undetectable levels. Remoistening of soils to field moisture over a 10-day period resulted in a significant (up to 0.06 mg l⁻¹) release of As in the pore water of soils containing >10 mg As kg⁻¹ soil, indicating the potential availability of As. In soils containing <5 mg As kg⁻¹, As was not detected in the pore water. A comparison of Bangladeshi soils with strongly weathered long-term As-contaminated soils from Queensland, Australia showed a much greater release of As in water extracts from the Australian soils. However, this was attributed to the much higher loading of As in these Australian soils. The correlation of pore water As with other inorganic ions (P, S) showed a strongly significant (P < 0.001) relationship with P, although there was no significant relationship between As and other inorganic cations, such as Fe and Mn. Batch sorption studies showed an appreciable capacity for both As^V and As^III sorption, with As^V being retained in much greater concentrations than As^III.